CN101182405B - Preparation method of dual-component aqueous polyurethane adhesive agent - Google Patents
Preparation method of dual-component aqueous polyurethane adhesive agent Download PDFInfo
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- CN101182405B CN101182405B CN2007100324299A CN200710032429A CN101182405B CN 101182405 B CN101182405 B CN 101182405B CN 2007100324299 A CN2007100324299 A CN 2007100324299A CN 200710032429 A CN200710032429 A CN 200710032429A CN 101182405 B CN101182405 B CN 101182405B
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- water
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- polyurethane dispersion
- rosin
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 44
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 43
- 239000000853 adhesive Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 52
- 229920003009 polyurethane dispersion Polymers 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 21
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 21
- 230000001070 adhesive effect Effects 0.000 claims abstract description 20
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 19
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 19
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 17
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 17
- 239000013530 defoamer Substances 0.000 claims abstract description 14
- 229920005862 polyol Polymers 0.000 claims abstract description 13
- 150000003077 polyols Chemical class 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 239000004970 Chain extender Substances 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract 12
- 239000011347 resin Substances 0.000 claims abstract 12
- -1 pentaerythritol ester Chemical class 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 150000002009 diols Chemical class 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- 229920005906 polyester polyol Polymers 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 2
- ZUQAPLKKNAQJAU-UHFFFAOYSA-N acetylenediol Chemical class OC#CO ZUQAPLKKNAQJAU-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims 1
- JRLZYKZRJOLHIJ-UHFFFAOYSA-N 2-prop-1-enoxyoxolane Chemical group O1C(CCC1)OC=CC JRLZYKZRJOLHIJ-UHFFFAOYSA-N 0.000 claims 1
- ULMZOZMSDIOZAF-UHFFFAOYSA-N 3-hydroxy-2-(hydroxymethyl)propanoic acid Chemical compound OCC(CO)C(O)=O ULMZOZMSDIOZAF-UHFFFAOYSA-N 0.000 claims 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 229940106012 diethylene glycol adipate Drugs 0.000 claims 1
- 125000005456 glyceride group Chemical group 0.000 claims 1
- 229920000921 polyethylene adipate Polymers 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 239000003995 emulsifying agent Substances 0.000 abstract description 3
- 239000002313 adhesive film Substances 0.000 abstract 1
- 239000000080 wetting agent Substances 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 239000012528 membrane Substances 0.000 description 9
- 238000010008 shearing Methods 0.000 description 8
- 230000008719 thickening Effects 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 239000004159 Potassium persulphate Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 235000019394 potassium persulphate Nutrition 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- WGACMNAUEGCUHG-VYBOCCTBSA-N (2s)-2-[[(2s)-2-[[(2s)-2-acetamidopropanoyl]amino]propanoyl]amino]-n-[(2s)-6-amino-1-[[(2s)-1-[(2s)-2-[[(2s)-1-[[(2s)-5-amino-1-[[(2s)-1-[[(2s)-1-[[(2s)-6-amino-1-[[(2s)-1-amino-3-(4-hydroxyphenyl)-1-oxopropan-2-yl]amino]-1-oxohexan-2-yl]amino]-3-hydroxy- Chemical compound CC(=O)N[C@@H](C)C(=O)N[C@@H](C)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CCCN=C(N)N)C(=O)N1CCC[C@H]1C(=O)N[C@@H](CO)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CCCN=C(N)N)C(=O)N[C@@H](CO)C(=O)N[C@@H](CCCCN)C(=O)N[C@H](C(N)=O)CC1=CC=C(O)C=C1 WGACMNAUEGCUHG-VYBOCCTBSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- VRAIHTAYLFXSJJ-UHFFFAOYSA-N alumane Chemical compound [AlH3].[AlH3] VRAIHTAYLFXSJJ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 108010074544 myelin peptide amide-12 Proteins 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 101100026251 Caenorhabditis elegans atf-2 gene Proteins 0.000 description 3
- 229920006387 Vinylite Polymers 0.000 description 3
- VLTOSDJJTWPWLS-UHFFFAOYSA-N pent-2-ynal Chemical compound CCC#CC=O VLTOSDJJTWPWLS-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229960004418 trolamine Drugs 0.000 description 3
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 2
- 102100039201 Constitutive coactivator of peroxisome proliferator-activated receptor gamma Human genes 0.000 description 2
- 101000813317 Homo sapiens Constitutive coactivator of peroxisome proliferator-activated receptor gamma Proteins 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- IWHMBXAAXBYCDD-UHFFFAOYSA-N dihydroxymethyl acetate Chemical compound CC(=O)OC(O)O IWHMBXAAXBYCDD-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 235000010985 glycerol esters of wood rosin Nutrition 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
本发明提供了一种双组分水性聚氨酯胶粘剂的制备方法。在反应设备中加入多异氰酸酯和低聚物多元醇反应，然后加入扩链剂反应得到聚氨酯预聚体，再加入中和剂和松香树脂中和；然后加水，用高速分散机分散乳化得到水性聚氨酯分散体；再均匀滴加乙烯基单体和引发剂反应得到松香和乙烯基树脂改性的水性聚氨酯分散体；向该松香和乙烯基树脂改性的水性聚氨酯分散体中加入消泡剂和润湿剂，再与多异氰酸酯固化剂混合得到双组分水性聚氨酯胶粘剂。本发明提高了水性聚氨酯胶粘剂的内聚强度和初粘力，降低了成本，消除了低分子乳化剂对胶膜的影响。The invention provides a preparation method of a two-component water-based polyurethane adhesive. Add polyisocyanate and oligomer polyol to the reaction equipment to react, then add chain extender to react to obtain polyurethane prepolymer, then add neutralizer and rosin resin to neutralize; then add water, disperse and emulsify with high-speed disperser to obtain water-based polyurethane Dispersion; then evenly drop vinyl monomer and initiator to react to obtain rosin and vinyl resin modified waterborne polyurethane dispersion; add defoamer and wetting agent to the rosin and vinyl resin modified waterborne polyurethane dispersion Wet agent, and then mixed with polyisocyanate curing agent to obtain two-component water-based polyurethane adhesive. The invention improves the cohesive strength and initial adhesion of the water-based polyurethane adhesive, reduces the cost, and eliminates the influence of the low-molecular emulsifier on the adhesive film.
Description
Technical field
The present invention relates to can be used for the preparation method of a kind of bi-component waterborne tackiness agent in fields such as automobile, wrapping material, timber, fiber, leather, specifically relate to a kind of preparation method of dual-component aqueous polyurethane adhesive agent.
Background technology
Urethane (PU) is the superpolymer that is polymerized by polyisocyanates (mainly being vulcabond) and oligomer polyol, owing to have strong polar carbamate groups, simultaneously between macromole, have hydrogen bond, thereby polyurethane material have characteristics such as high strength, wear-resisting, anti-solvent; In addition, the structure by changing polyol, molecular weight etc., the performance that can also in a big way, regulate polyurethane material.Polyurethane material has obtained in fields such as rubber, plastics and synthon using widely now.
Urethane can be divided into solvent borne polyurethane and non-solvent urethane.The organic solvent type polyurethane has that solvent is volatile, smell is big, polluted air, easy firing, can cause the defective to aspects such as the murder by poisoning of human body and danger, has limited it and has further used.In recent ten years, the cry of the public opinion of preserving the ecological environment grows with each passing day, and some developed countries have formulated fire codes and solvent rules in succession, the use of restriction solvent-based adhesive, and this just makes the exploitation of aqueous adhesive become inevitable trend.Aqueous polyurethane has that resistance to low temperature is good, snappiness is good, bonding strength is high, do not fire, nontoxic, free from environmental pollution, save advantage such as the energy, therefore become the heat subject of domestic and international research.The existing abroad quite development of aqueous polyurethane is all used to some extent in a lot of fields; But at home, the aqueous polyurethane emulsion tackiness agent is owing to be subjected to the imported raw material price limit, and theoretical still applied research all lags behind very much, and output is very little, kind is single, does not satisfy the domestic market far away to the growing demand of this high-quality environment protective type tackiness agent.Along with the production domesticization and the production-scale expansion of the raw material of producing aqueous polyurethane, the price of raw material will reduce gradually, this just make aqueous polyurethane research and be applied in the domestic huge development opportunity that has.Can predict, following tackiness agent market must be the world of pollution-free, nontoxic environment-friendly adhesive, and in the aqueous adhesive, the aqueous polyurethane of excellent performance will be come out top.Therefore carry out the theory and the applied research of environment-friendly water-based polyurethane tackiness agent, have very big economic benefit and environmental benefit.
Yet single water-based polyurethane adhesive cohesive strength is height not too, can not satisfy the needs of high strength bonding requirement, must be to its modification.The present invention adds the water-based polyurethane adhesive that a kind of solidifying agent obtains two-pack, can satisfy the needs of multiple material adhesive.
Summary of the invention
The object of the invention is to provide a kind of preparation method of dual-component aqueous polyurethane adhesive agent.
For achieving the above object, the present invention has taked following technical scheme:
The preparation method of a kind of dual-component aqueous polyurethane adhesive agent of the present invention is characterized in that, may further comprise the steps:
(1) preparation of base polyurethane prepolymer for use as: in conversion unit, add polyisocyanates and oligomer polyol, react 2～3h down at 60～80 ℃, add chainextender reaction 2～5h then, obtain base polyurethane prepolymer for use as, in this base polyurethane prepolymer for use as, add neutralizing agent and Gum Rosin, in and 10～20min, degree of neutralization is 85～100%, wherein, the ratio of polyisocyanates and oligomer polyol amount of substance is: 2.8～1.2: 1, and Gum Rosin: polyisocyanates: the mass ratio of chainextender is 2～5: 20: 3.5～5;
(2) aqueous polyurethane dispersion is synthetic: add water in the base polyurethane prepolymer for use as after the neutralization that step (1) obtains, with high speed dispersor speed dispersion and emulsion 10～30min with 2500～4500rpm/min under 35 ℃～40 ℃, obtain aqueous polyurethane dispersion, the quality of described water is 30～35% for making this aqueous polyurethane dispersion solid content;
(3) in the aqueous polyurethane dispersion that step (2) obtains, evenly drip vinyl monomer and initiator, 70～75 ℃ of reaction 3～4h are warming up to 80～90 ℃ again, reaction 1～1.5h, cooling again, discharging and filtration obtain rosin and Vinylite modified waterborne polyurethane dispersion; Described vinyl monomer: the solid ingredient of aqueous polyurethane dispersion: the mass ratio of initiator is 10～25: 100: 0.1～0.3;
(4) in Gum Rosin that step (3) obtains and Vinylite modified waterborne polyurethane dispersion, add defoamer and flow agent, mix with polyisocyanate curing agent again, obtain dual-component aqueous polyurethane adhesive agent, wherein Gum Rosin and Vinylite modified waterborne polyurethane dispersion: defoamer: flow agent: the mass ratio of polyisocyanate curing agent is 100: 0.1～1: 0.1～0.5: 1～15.
The polyisocyanates of described step (1) be tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, ditan-4,4 '-vulcabond, poly methylene poly phenyl poly isocyanate or xylylene diisocyanate.
The oligomer polyol of described step (1) comprises polyester polyol or polyether glycol.
The oligomer polyol of described step (1) also comprises polybutadiene diol, described polyester polyol comprises polyethylene glycol adipate glycol, poly-hexanodioic acid glycol ether esterdiol, poly-hexanodioic acid-1,4-butanediol ester glycol, glycol ether esterdiol, polycarbonate diol or polycaprolactone glycol; Described polyether glycol comprises polyoxypropyleneglycol, polyoxytrimethylene triol, polytetrahydrofuran diol or tetrahydrofuran (THF)-propylene oxide copolymerization glycol.
The wetting ability chainextender of described step (1) is dihydroxymethyl acetate, dimethylol propionic acid or dimethylolpropionic acid.
The Gum Rosin of described step (1) is ester gum, pentalyn or rosin MALEIC ANHYDRIDE ester.
The neutralizing agent of described step (1) is triethylamine or trolamine.
The vinyl monomer of described step (3) is methyl methacrylate, butyl acrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate or ethyl propenoate.
The initiator of described step (3) is Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate or benzoyl peroxide.
The flow agent of described step (4) is an acetylenediol class flow agent, comprises that model is the flow agent of SAN1 or SAN2; Defoamer is the silicone oil defoamer, comprises that model is the defoamer of ATF-1 or ATF-2; Polyisocyanate curing agent comprises that model is the polyisocyanate curing agent of PUDS80, PUDS81 or PUDS82.
With respect to prior art, the present invention has following advantage:
(1) Gum Rosin and vinyl monomer are introduced in the modification of polyurethane adhesive simultaneously, improved the initial bonding strength of water-based polyurethane adhesive, reduced the cost of synthetic tackiness agent, made the polyurethane adhesive of synthetic modification have the performance of Gum Rosin, acrylate and urethane.
(2) whole process using self-emulsification carries out letex polymerization and need not add emulsifying agent in emulsion polymerization process, has eliminated the influence of low molecule emulsifying agent to glued membrane;
(3) add solidifying agent, obtain dual-component aqueous polyurethane adhesive agent.
(4) the two-pack modified waterborne polyurethane tackiness agent of the present invention's preparation, its performance is suitable with the performance of external similar water-based polyurethane adhesive, and cost is more much lower than external sample.
Embodiment
For better understanding the present invention, the present invention is done detailed description further below in conjunction with embodiment.The scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1
With 100g TDI, 246g molecular weight be 1000 polyoxypropyleneglycol at 60 ℃ of reaction 2h, add the 17.5g dimethylol propionic acid then, reaction 2h gets base polyurethane prepolymer for use as; In this performed polymer, add the 11.2g triethylamine, add the 10g pentalyn then, in and the time be 10min, the neutral base polyurethane prepolymer for use as.Be cooled to 35 ℃ then, under the 2500r/min rotating speed, add 870g water, disperse 10min, obtain aqueous polyurethane dispersion.Evenly drip 38g methyl methacrylate and 0.38g Potassium Persulphate in this aqueous polyurethane dispersion, 70 ℃ of reaction 3h were warming up to 80 ℃ of insulation reaction 1 hour again, reduced to room temperature, and discharging is also filtered, and promptly obtains aqueous polyurethane dispersion.
With adding 1g flow agent SAN2,0.5g defoamer ATF-2 in the above-mentioned aqueous polyurethane dispersion that makes of 100g, mix with 1g solidifying agent PUDS80 again, stir, promptly obtain two-pack modified waterborne polyurethane tackiness agent.
These product performance relatively see Table 1 with external certain company's product performance.
Table 1
| Performance index | External certain company's product | The product of present embodiment |
| Solid content, % | 35 | 35 |
| Rotary viscosity (not thickening) mPa.s | 45 | 46 |
| The glued membrane tensile strength, MPa | 12 | 12.3 |
| 180 ° of stripping strengths (glued board-leatheroid) N.mm -1 | 4.2 | 4.3 |
| Shearing resistance (aluminium-aluminium) MPa | 8.5 | 8.4 |
As shown in table 1, the present invention introduces rosin and vinyl monomer in the water-based polyurethane adhesive modification simultaneously, adds solidifying agent simultaneously, obtains dual-component aqueous polyurethane adhesive agent.The product of present embodiment preparation is rotary viscosity, glued membrane tensile strength, 180 ° of stripping strengths of tackiness agent when thickening not, and shearing resistance and external product are basic identical, but this product adopts domestic starting material mostly, can satisfy the demand of multiple interior trim of automobile and structure glue, and total cost is more much lower than external like product, preparation technology simple, be easy to promotion and application.
Embodiment 2
The polyhutadiene esterdiol of 100g HDI, 403g adds 25g dihydroxymethyl acetate then at 70 ℃ of reaction 2h, and reaction 2h gets base polyurethane prepolymer for use as; In this performed polymer, add the 27.3g triethylamine, add the 25g ester gum then, in and the time be 20min, the neutral base polyurethane prepolymer for use as.Be cooled to 40 ℃ then, under the 4500r/min rotating speed, add 1400g water-dispersion 30min, get aqueous polyurethane dispersion.Evenly drip 150g ethyl propenoate and 0.9g Potassium Persulphate in this aqueous polyurethane dispersion, 75 ℃ of reaction 3h are warming up to 85 ℃ of insulation reaction 1.2h again, reduce to room temperature, and discharging is also filtered, and promptly obtains aqueous polyurethane dispersion.
To add 0.1g flow agent SAN1 in the above-mentioned aqueous polyurethane dispersion that makes of 100g, 0.1g defoamer ATF-1 mixes with 5g solidifying agent PUDS81 again, stirs, and promptly obtains two-pack modified waterborne polyurethane tackiness agent.
These product performance relatively see Table 2 with external certain company's product performance.
Table 2
| Performance index | External certain company's product | The product of present embodiment |
| Solid content, % | 35 | 37 |
| Rotary viscosity (not thickening) mPa.s | 45 | 46 |
| The glued membrane tensile strength, MPa | 12 | 13.8 |
| 180 ° of stripping strengths (glued board-leatheroid): N.mm -1 | 4.2 | 5.0 |
| Shearing resistance (aluminium-aluminium) MPa | 8.5 | 9.6 |
As shown in table 2, the present invention introduces rosin and vinyl monomer in the water-based polyurethane adhesive modification simultaneously, adds solidifying agent simultaneously, obtains dual-component aqueous polyurethane adhesive agent.The product of present embodiment preparation is rotary viscosity, glued membrane tensile strength, 180 ° of stripping strengths of tackiness agent when thickening not, and shearing resistance and external product are basic identical, but this product adopts domestic starting material mostly, can satisfy the demand of automotive trim and structure glue, and total cost is more much lower than external like product, preparation technology simple, be easy to promotion and application.
Embodiment 3
The polyethylene glycol adipate glycol of 100g IPDI, 353g adds the 20g dimethylolpropionic acid then at 80 ℃ of reaction 3h, and reaction 5h gets base polyurethane prepolymer for use as; In this performed polymer, add the 18.7g trolamine, add the 15g pentalyn then, in and the time be 20min, the neutral base polyurethane prepolymer for use as.Be cooled to 40 ℃ then, under the 4500r/min rotating speed, add 941g water, disperse 30min, get aqueous polyurethane dispersion.Evenly drip 100g Propylene glycol monoacrylate and 0.5g Potassium Persulphate in this aqueous polyurethane dispersion, 75 ℃ of reaction 4h are warming up to 90 ℃ of insulation reaction 1.5h again, reduce to room temperature, and discharging is also filtered, and promptly obtains aqueous polyurethane dispersion.
With adding 0.5g flow agent SAN1,0.25g defoamer ATF-2 in the above-mentioned aqueous polyurethane dispersion that makes of 100g, mix with 10g solidifying agent PUDS82 again, stir, promptly obtain two-pack modified waterborne polyurethane tackiness agent.
These product performance relatively see Table 3 with external certain company's product performance.
Table 3
| Performance index | External certain company's product | The product of present embodiment |
| Solid content, % | 35 | 38 |
| Rotary viscosity (not thickening) mPa.s | 45 | 48 |
| The glued membrane tensile strength, MPa | 12 | 14.2 |
| 180 ° of stripping strengths (glued board-leatheroid): N.mm -1 | 4.2 | 5.2 |
| Shearing resistance (aluminium-aluminium) MPa | 8.5 | 10.1 |
As shown in table 3, the present invention introduces rosin and vinyl monomer in the water-based polyurethane adhesive modification simultaneously, adds solidifying agent simultaneously, obtains dual-component aqueous polyurethane adhesive agent.The product of present embodiment preparation is rotary viscosity, glued membrane tensile strength, 180 ° of stripping strengths of tackiness agent when thickening not, and shearing resistance and external product are basic identical, but this product adopts domestic starting material mostly, can satisfy the demand of the multiple interior trim structure glue of automobile, and total cost is more much lower than external like product, preparation technology simple, be easy to promotion and application.
Embodiment 4
The polybutadiene diol of 100g XDI, 415g adds the 22g dimethylol propionic acid then at 72 ℃ of reaction 2.5h, and reaction 2.5h gets base polyurethane prepolymer for use as; In this performed polymer, add the 21.7g trolamine, add 20g rosin MALEIC ANHYDRIDE ester then, in and the time be 16min, the neutral base polyurethane prepolymer for use as.Be cooled to 33 ℃ then, under the 3900r/min rotating speed, add 1232g water, disperse 23min, get art based polyurethane dispersion.Evenly drip 116g ethyl propenoate and 0.7g Potassium Persulphate in this aqueous polyurethane dispersion, 73 ℃ of reaction 2.5h are warming up to 81 ℃ of insulation reaction 1.1h again, reduce to room temperature, and discharging is also filtered, and promptly obtains aqueous polyurethane dispersion.
With adding 0.7g flow agent SAN2,0.4g defoamer ATF-1 in the above-mentioned aqueous polyurethane dispersion that makes of 100g, mix with 6.3g solidifying agent PUDS80 again, stir, promptly obtain two-pack modified waterborne polyurethane tackiness agent.
These product performance relatively see Table 4 with external certain company's product performance.
Table 4
| Performance index | External certain company's product | The product of present embodiment |
| Solid content, % | 35 | 34 |
| Rotary viscosity (not thickening) mPa.s | 45 | 43 |
| The glued membrane tensile strength, MPa | 12 | 11.3 |
| 180 ° of stripping strengths (glued board-leatheroid): N.mm -1 | 4.2 | 3.9 |
| Shearing resistance (aluminium-aluminium) MPa | 8.5 | 8.0 |
As shown in table 4, the present invention introduces rosin and vinyl monomer in the water-based polyurethane adhesive modification simultaneously, adds solidifying agent simultaneously, obtains dual-component aqueous polyurethane adhesive agent.The product of present embodiment preparation is rotary viscosity, glued membrane tensile strength, 180 ° of stripping strengths of tackiness agent when thickening not, and shearing resistance and external product are basic identical, but this product adopts domestic starting material mostly, can satisfy the demand of automotive trim and structure glue, and total cost is more much lower than external like product, preparation technology simple, be easy to promotion and application.
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